High-porosity cellular catalyst having acidic properties to modify colophony

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.

EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.

5 ex


The present invention relates to a process for producing products of natural resins, such as rosin, and more narrowly to the modification of rosin.

Rosin is a product of primary processing of natural resins, primarily pine oleoresin, and is widely used in various industries. The lack of natural rosin is a high content of unsaturated resin acids, mainly abietic prone to oxidation by the oxygen of the air and the change of physico-chemical properties over time. To overcome this drawback using mainly two methods of modification of rosin: hydrogenation and disproportionation.

Disproportionately rosin significantly more resistant to air oxidation, obtained on the basis of her Soaps are used as emulsifiers for cold polymerization in the production of synthetic rubbers. Disproportionately rosin is also used in the manufacture of adhesives, insulating materials in electrical engineering and for other purposes.

The changing composition of rosin in the disproportionation (reducing the number of acids with conjugated double bonds and the formation of dehydro-, dihydro - and tetrahydroborate) due to the reactions of hydrogenation and dehydrogenation. The latter processes occur when the appreciation is the R temperatures in the presence of various catalysts. Since at high temperatures intensifying processes decarboxylation, leading to deterioration in the quality of the rosin, and the accumulation of gaseous hydrogen, try to decrease this parameter.

The main catalysts for the disproportionation at the present time are the following:

1) iodine, in pure form or with promoters (patent 299080, the Netherlands; patent 2060637, England). The disadvantages of these catalysts are the high cost of iodine, environmental pollution by the products of its transformation (including alkylidene) and the iodine, a significant decrease in acid number, due to decarboxylation at high process temperatures;

2) sulfur and selenium, their oxides and compounds with different media, for example, zeolites (A.S. USSR 763420, Sanderman Century Natural resins, turpentine, taly oil. - M.: Forest industry, 1964, s.257-260). The disadvantages of these catalysts are dark rosin, high toxicity of selenium

3) solid-phase hydrogenation catalysts: mainly metals of the VIII group of the Mendeleev periodic table of elements. The use of Nickel is limited because of its relatively low catalytic activity. In addition, its ability to dissolve the rosin leads to the need for additional purification (distillation) rosin;

4) the biggest rasprostrannyayuschie catalysts based on palladium, the first patents for which were obtained in the 30-ies of the last century. The most famous are the catalysts containing active element is palladium deposited on activated carbon (U.S. Pat. Russia 2055848 and 2081143).

As the catalyst can also be used ion-exchange resin of acid nature (A.S. USSR 1344772).

Gidrirovanny rosin lighter than the original rosin, which determines the possibility of its use in the manufacture of optical glue for lenses, coatings for optical instruments. Wide application gidrirovanny rosin finds in the manufacture of synthetic rubbers, particularly in the production of products that do not contain particulate fillers.

Hydrogenation of rosin exercise for nearly 100 years. The main industrial method currently are catalytic processes. As active agents used Nickel (U.S. Pat. USA 2155039, 2174651, 2739947), rhodium and palladium (U.S. Pat. USA 2346793, 2367287) catalysts. The consumption of hydrogen in the hydrogenation process is 2 mol per one mol of abietic acid.

As a prototype we have chosen the patent of Russia 2055848, according to which for modification (disproportionation) of rosin mixed use catalyst: socialization - cured dehydrated islamochristiana clay Benton is a Hilbert-type and catalyst - palladium charcoal. Melt the rosin is passed sequentially through socialization and then through the catalyst. This provides a residual content of abietic acid at the level of 1-2% at high acid number (there is a slight, 1-3 units decrease in comparison with the original product). The temperature in the catalyst zone 220°C. According to the examples in the patent, the mixing rosin is argon, which leads to significant economic costs. The process was complicated by the destruction and entrainment of catalyst (palladium carbon, which is accompanied not only by a decrease in its catalytic activity, but also by the necessity of separating the resulting product from the fragments of the catalyst.

The object of the present invention is a highly porous honeycomb catalyst with acid properties for modification of rosin. As the base catalyst used highly porous cellular carrier of aluminum oxide (α-Al2About3), and as the active component is characterized by high acidity of sulfated oxides of metals of group IV (TiO2, ZrO2and others) and palladium metal.

Highly porous cellular carrier for catalyst made from open-celled polyurethane foam, soaking the last slip, containing them for more than 30% α -Al2About3, followed by drying at 100 to 200°and annealing at a temperature of 1300-1500°C. during this treatment, the organic basis of completely dries out. The resulting highly porous carrier contains more than 90% α-Al2About3. To develop the surface of the catalyst on its surface causing the oxides of metals of group IV of the Mendeleev periodic Table of elements. For this purpose, the carrier is impregnated with solutions of water soluble salts of zirconium, for example chloride Zirconia or nitrate Zirconia, or a mixture of tetraethoxysilane with isopropyl alcohol, dried at 100-200°and calcined at a temperature of 450 to 950°C. the Content of metal oxide in the catalyst after these operations is 4-10%.

The samples impregnated with a solution of 5-10% sulfuric acid and after drying annealed at a temperature of 550-650°C. the Increase in weight of the catalyst after these operations should be 1-2%.

When further treated with a solution of palladium nitrate, drying and calcination at 450-550°on the surface of the catalyst are 0.5-5% of the oxide of palladium, which, after recovery of molecular hydrogen at room temperature is transformed into metallic palladium.

Produced by this technology the catalyst has a density of 0.3-0.4 g/cm3that corresponds to the porosity of 90-93%, microporosity 20-30%, with the tournament pore size - 0.5 to 2 μm, the mechanical strength of 0.5-2 MPa.

The use of highly porous honeycomb catalyst designed as a single unit, through which passes a flow of rosin and nitrogen or hydrogen, on the one hand, due to the developed surface provides high speed modification, on the other hand, due to the high mechanical strength almost completely eliminates grinding and entrainment of the catalyst.

It is known that solid sulfated oxides of metals of group IV of the Periodic table have a catalytic effect on many electrophilic reactions of the type and in recent years has been widely tested as catalysts in various processes (Krylov, O.V. Solid-phase catalysts. M: ICC academkniga, 2004). Their preparation and properties are discussed in detail in the review Ivanov A.V., Cosnova L.M. Solid supercolony on the basis of zirconium oxide. Grew up with. chem. journal, 2000. T. No. 2. P.21-52, article M. Hino, K. Arata, J. Chem. Soc. Chem. Comm 1980. R-852 and several other publications. However, their independent use in the process of modification of rosin, according to our data, does not provide the necessary positive effect.

The process of modification of rosin successfully runs only when sharing sulfated oxides of high acidity (such as TiO2or ZrO2) and palladium metal; when used is the so called desulfation oxides (TiO 2that α-Al2O3together with palladium degree of disproportionation also dramatically reduced (example 34).

In addition to the above-mentioned advantages of the modular catalyst: no grinding and, therefore, contamination of rosin its fragments, increase service life, the proposed method allows to reduce the temperature of the process of disproportionation 30-40°C. consequently, the reduced decarboxylation of resin acids. A similar positive effect was achieved in the reaction of an alcohol solution of rosin with this catalyst in a hydrogen environment, the lack of the latter (examples 5 and 6).

The method of preparation of the catalyst and the effectiveness of the proposed catalyst of its application can be confirmed by the following examples.

Example 1

Preparation of open-celled polyurethane foam is made in the form of a cylinder with a diameter of 50 mm and a height of 50 mm was impregnated with the slurry containing 40% α-Al2About3method of cyclic compression and tension, followed by drying at 100 to 200°and annealing at a temperature of 1300-1500°C. during this treatment, the organic basis of completely dries out. The resulting highly porous carrier contains more than 90% α-Al2About3. Then the carrier was impregnated at room temperature with 15% NaCl Zirconia in the water and then you argali at a temperature of 950° C for 1 hour. The content of metal oxide in the catalyst was 7.5%.

The sample obtained at room temperature was soaked with a solution of 10% sulfuric acid (by immersion and subsequent runoff of excess acid without external influence) and after drying was probalily at a temperature of 550-650°C. the Increase in weight of the catalyst after this operation amounted to 1%.

When further treated with a solution of 5% palladium nitrate, drying at 120°C and calcination at 450-550°C on the surface of the catalyst was applied to 2.35% of the oxide of palladium, which, after recovery of molecular hydrogen at room temperature turned into metallic palladium.

Produced by this technology the catalyst contains a 2.0% Pd, has a density of 0.3-0.4 g/cm3that corresponds to the porosity of 90-93%, microporosity 20-30%, the average pore size is 0.5 to 2.0 μm, the mechanical strength of 0.5-2.0 MPa.

In a heated cylindrical reactor with an inner diameter of 50 mm and a volume of 400 ml was placed highly porous honeycomb catalyst in the form of a single block, fixed in the middle of the device. The mass of the catalyst 30 g, the density of 0.38 g/cm, the content of sulfated Zirconia is 8.5%, the content of palladium metal - 2%. In the lower part of the vertically installed reactor load of 25 g of rosin content of abietic sour is 45%, acid number - 172 and create a nitrogen pressure of 0.2 MPa. Turn up the heat and bring the temperature inside the reactor up to 180°C. Then transferred to the reactor in a horizontal position and include longitudinal mixing (rocking). Duration of response 135 minutes, the Apparatus is cooled to 100°With, relieve gas pressure and unload rosin. The content of abietic acid and 0.1%, acid number - 168, color - W.

Example 2

Similar to example 1. Process temperature 190°C. the Content of abietic acid rosin after the experience of 1.6%.

Example 3.

In the same reactor loaded the unit of catalyst, made of α-Al2O3covered with surface γ-Al2About3total weight 32,4 g, a density of 0.41 g/cm3the content of metallic palladium is 2.6%, and the remaining conditions are identical to example 1. The content of abietic acid rosin after the reaction of 18%.

Example 4.

In the same reactor was loaded with 100 ml of ethanol and 8 g of rosin, the catalytic unit total weight of 31.3 g, the composition of the catalyst similar to the catalyst of example 1, but the content of metallic palladium to 2.8%. The initial hydrogen pressure - 0.17 MPa. The temperature of the experience 115°With, the process time 25 min Flow of hydrogen was 0.92 mol per 1 mol of abietic acid rosin. The content of abietic acid after the reaction is 0%.

Example 5.

Similar is n example 4, but loading a container 12, an Initial hydrogen pressure of 0.3 MPa. The flow of hydrogen to 1.1 mol per mol of abietic acid rosin. The content of abietic acid after the reaction is 0%.

The catalyst for the modification of rosin, characterized in that as the carrier using high porous foam block material based on α-Al2About3and as an active part of the catalyst is sulfated metal oxide of group IV and metal palladium.


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